Copolymers of aryl olefins and alpha beta ethylenically unsaturated carboxylic acid esters of oxidized nonfrosting siccative oils



United COPOLYMERS OF ARYL OLEFINS AND ALPHA BETA ETHYLENKCALLYUNSATURATEI) CAR- BOXYLIC ACID ESTERS OF PXIDIZED NON- FROSTINGSICCATIVE GEES No Drawing. Application August 29, 1952, Serial No.307,175

23 Claims. (Cl. 260 -2c This application is a continuation in part ofour application Serial No. 240,798, filed August 7, 1951, now abandoned,entitled Copolymers of Aromatic Olefins and Alpha Beta UnsaturatedDicarboxylic Acid Esters of Oxidized Siccative Oils.

-T his invention relates to copolymers of aryl olefins and alpha betaethylenically unsaturated carboxylic acid esters of oxidized nonfrostingsiccative oils. More Particularly, the invention relates to theproduction of such copolymers which are capable of use in the productionof coatings and which are particularly adapted for use in themanufacture of floor coverings as a binder for the floor covermg.

Copolymers of aryl olefins, such as styrene, with esters of fatty oils,are known in the art. For example, Tawney in Patent 2,505,844 disclosesthe production of copolymers of castor oil maleates with mono-olefiniccompounds such as styrene. However, such a copolymer cannot be used toproduce a suitable floor covering material by commercially acceptablemethods.

We have found that aryl olefins may be reacted with alpha betaethylenically unsaturated carboxylic acid esters of oxidized nonfrostingsiccative oils to produce materials which may be compounded withpigments and fillers and possess excellent properties as a floorcovering.

In accordance with our invention, any ofa number of aryl olefins may beemployed in carrying out the reaction. For example, the aryl olefin maybe styrene, orthomethyl styrene, metamethyl styrene, paramethyl styrene,

ethyl styrene, dimethyl styrene, alpha methyl styrene,'

parachlorostyrene, paramethoxy styrene, and the like. Generallyspeaking, particularly advantageous results have been obtained whenstyrene is the aryl olefin which is reacted with the ester of oxidizednonfrosting siccati e oil. These aryl olefins are all well known vinylaromatic compounds having the group Among the alpha beta 'ethylenicallyunsaturated carboxylic acids which we may employ'in producing the esterof oxidized oil are such dicarboxylic acids as maleic acid, fumaricacid, itaconic acid, and the like; and such monocarboxylic acids asacrylic acid, methacrylic acid, crotonic acid, sorbic acid, and thelike. It is also within the scope of our invention to use cyclicaliphatic acids such as tetrahydrophthalic acid, which is an adduct ofmaleic acid and butadiene, the adducts of cyclopentadiene Our inventiondoes not con- Patent template nondrying oils which, for the purposes ofour invention, include material such as castor oil, inasmuch asnondrying oils are incapable of producing materials which possess thecharacteristics required of materials used as binders for floorcoverings. Likewise, our invention does not contemplate the use offrosting drying oils such as China-Wood oil, oiticica oil, and the like,because of the temperatures contemplated in the oxidation step of theprocess of our invention. Generally speaking, the temperatures arebetween room temperatures and heat bodying temperatures in order toobtain high oxidation with relatively low viscosity. When frosting oilsare utilized under such conditions, theviscosity builds up too rapidlyto permit obtaining the desired oxidation. The siccative oils used toadvantage in the practice of our invention are those containingsubstantial quantities of linoleic acids. Generally speaking, thepreferred oils contain at least about 35% natural nonconjugatedlinole'ic acid and/ or linolenic acid.

The oxidized oils are prepared under such conditions that a minor amountof polymerization takes place. This is accomplished by agitating thesiccative oil in air in the presence of driers, such .as napthenates,tallates and/or octoates of lead and/or manganese at a temperature suchas bout 40 C. to about 150 C., advantageously about 60 C. to about C.The oxidation is conducted to a viscosity above about 12 secondsGardner- Holdt at 25 C. Generally speaking, we prefer to maintain .theviscosity at not more than about 25 to 30 seconds Gardner-Holdt. Thisindicates that the conditions of oxidation are such that littlepolymerization has taken place. The oxidized oils are prepared in such amanner as to produce materials having a hydroxyl number in the range ofabout 30 to about 50. The hydroxyl numbers indicate the presence ofhydroxyl groups resulting from oxidation of the unsaturated fatty acidchains and not from hydrolysis of the ester. In oxidation of the oils,peroxides are formed which'decompose to give the hydroxyl groups.

In the esterifica-tion of the thus oxidized oils, the nonfrostingoxidized siccative oil is advantageously refluxed with the alpha betaethylenically unsaturated c-arboxylic acid or its anhydride. Therefluxing is generally carried out while the reactants are dispersed inan inert hydro carbon solvent, such as benzene, toluene, xylene, and thein such proportions that the hydroxyl and carboxyl groups are present inapproximately stoichiometrically equivalent ratios. In other words, weuse .1 to .5 mol of alpha beta acid per fatty acid chainor acyl radical.Too much acid may cause excessive gel formation on subsequentesterification.

Esterfication is continued with or without catalysts,

such as sulfuric acid, with removal of water until the acid number isreduced, preferably to about 15 or below.

In producing the copolymer, the aryl olefin constitutes about 33% toabout 67%- of the polymerizable mixture,

the balance being the oxidized oil ester. Generally speaking, we find itadvantageous to effect the polymerization by heating the reactants atelevated temperatures,

such as about 60 to aboutl50 C., advantageously at temperatures of about100 C. to about Particularly advantageous results have been obtained bypolymerizing a mixture containing about equal parts "by weight of arylolefin and oxidized oil. We prefer to efiect copolymerization byrefluxing the oxidizednonfrosting siccative oil ester with the arylolefin While dis-t Generally, the solvent is the same as that used inthe esterification'stage' persed in an inert hydrocarbon solvent.

Our invention may be more readily" understood by reference to thefollowing specific examples, in which a comparison is made with productsobtaind by forming V copolymers of styrene and caster oil esters.

Example I 200: grams of castor oil. and 21. grams of maleic anhydridewith 200ml. of carbon tetrachloride were refluxed for 6 hours- Theacidnumber was: then 77. The mixture. was styrenated with. 57.4 grams ofstyrene and 4.13 grams of benzoyl peroxide. On removal of the solvent,alight-colored gelled product was obtained which formed a sheet withwood flour and whiting, the usual fillers, that did not cure in 30 days.

The above examples illustrate the type of product obtained by reactinghydoxyl containing nondrying oil esters with aryl olefins. In suchv oilsas castor oil, the hydroxyl groups are present initially in the oil. Thesame effect may be. obtained from oils in which hydroxyl groups areintroduced by alcoholysis of the oil with polyols, such as glycol,glycerol, pentaerythritol, and the like.

Example III 200 grams of oxidized soya bean oil having a viscosity of13.1 seconds Gardner-Holdt, 3 grams of maleic anhydride, and 200 ml. oftoluene were refluxed for 6 hours at 110 C. to 115 C. The resultingester was styrenated' by refluxing with 200 grams of styrene and 2 gramsof benzoyl peroxide. A homogeneous, clear, light-colored binder materialwas obtained. This formed a sheet with the usual fillers and cured in460 hours. The indentation was 27.2%, and the bend break angle of thesheet was 37.

Example IV 200 grams of oxidized soya bean oil from the same batch aswas used in Example IH were treated with 21 grams of maleic anhydride in200 ml. of carbon tetra.- chloride' and. refluxed, for 6 hours. At theend of. that time, an insoluble gel had formed and no attempt was madeto styrenate it.

Generally speaking, it is advantageous to carry out the reactionin. thepresence of aromatic hydrocarbon solvents, such as toluene. Theadvantages of' such solvents over. those such as. carbon. tetrachlorideare illustrated by comparing Example 111 with Example IV..

Example V 200 grams of soya bean oil oxidized to a viscosity of18'seconds at 30 C. Gardner-Holdt, 3.52 grams of acrylic acid, and 200ml. of toluene were heated at 110 C. for 6 hours. 200 grams ofstyreneand 2 grams of benzoylperoxide were added in 200 ml. toluene andthemixt-ure was heated at 110"" C. for 5 hours. The solvent was re--moved at reduced pressure and a clear, tough, thermoplastic gel wasobtained.

In the practice of'our invention, itis essential to avoid gel formationin the first stage of' the reaction; This may be done by controlling'theamount of alpha betaethylenically unsaturated .carboxylic acid ester inthe mixture subjected to polymerization conditions, and also bycontrolling the conditions of oxidation of the oil;

In producing a floor covering binder from the copolymers of. ourinvention, a mixture of about 5% to about '15 by weight of a resin suchas ester gum, rosin-modifie'd phenobformaldehyde resin, diethyleneglycol ester of hydrogenated rosin, and the like, and about to about 85%of our copolymer may be used. The resin serves as a tackifying agent forthe binder composition. Of course, conventional pigments, fillers, andthe like may be admixed with the binder in proportions of about 30% toabout 40% binder and about 70% to about 60% filler and pigment toproduce a flooring composition.

This embodiment of our invention is illustrated. by the followingexamples:

. Example VI 175 gramsofoxidized soybean oil, hydroxyl number 56,

were esterified to an acid number of18.6 by'heati-ngwith 2.6 grams offumaric acid in a refluxing toluene solution for eight hours.Styrenation was effected by refluxing a mixture of the esters withv anequal quantity of styrene in toluene solution, using 1% benzoyl peroxideas a catalyst. Ten per cent ester gum was added as a modifier and thetoluene was removed by reduced pressure distillation, The sheet preparedfrom this product according to the usual linoleum procedure cured in 412hours to an ind'entation of 37%, bend-break anglev 34. Excellent alkaliresistance was shown by the usual alkali indentation tests in which thesheet hardened slightly upon exposure to dilute alkali, change inindentation was 4.9%. This compares with a value of +10.9% for linoleum.

Example VII grams of oxidized soybean oil, Gardner-Holdt viscosity46sec, were esterified with 1.5 grams of maleic' of 39. During thealkali'resistance test it was'noted that there was less softening of thesheet than with linoleum prepared from the usual binder. change inindentation was 7.8%; linoleum sheets showed achange of The alkaliindentation, the indentation, and the bend-- break angle referred toherein were determined in accordance with procedures described in UnitedStates Patent No. 2,561,427. 7

' The copolymers of our invention may also be used as ingredients ofcoating compositions; for example, print paints employed in themanufacture of printed felt ba'se floor coverings. The products ofourinvention may also be employed as protective coatings which can beapplied by brush, spray, and the like, to wood, glass, metal, and thelike, and air dried or'baked toform a clear homogeneous film. Thesecoatings are characterized byexcellent alkali resistance and waterresistance.

This embodiment of our invention is illustrated by the followingspecific example:

Example VIII neous solution was applied to a glass plate. andair driedat room temperature to givea clear homogeneous film.

Ifidesire'd, the usual reinforcing resins employed in the coating artmaybe added to the coatings of our invention. Examples of suchreinforcing resins are melamineformaldehyde. resins, phenol-formaldehyderesins, ureaformaldehyde resins, and the like.

We claim: I 1'. A method of'producin'g valuable polymers comprisingesterifying a mixturethe reactive ingredients of' consist of an oxidizednonfrosting vegetable siccative oil having a viscosity of not more thanabout 30 seconds on the Gardner-Holdt scale and an alpha betaethylenically unsaturated carboxylic acid and copolymerizing theresulting ester with a compound consisting of a vinyl aromatic compoundhaving a single vinyl group at elevated temperatures of about 60C. toabout 150 C.

2. A method of producing valuable polymers comprising refluxing amixture the reactive ingredients of which consist of an oxidizednonfrosting vegetable siccative oil having a viscosity of not more thanabout 30 seconds on the Gardner-Holdt scale and an alpha betaethylenically unsaturated dicarboxylic acid while dispersed in ahydrocarbon solvent and copolymerizing the resulting ester with acompound consisting of a vinyl aromatic compound having a single vinylgroup in the presence of a hydrocarbon solvent at elevated temperaturesof about 60 C. to about 150 C.

3. A method of producing valuable polymers comprising refluxing amixture the reactive ingredients of which consist of an oxidizednonfrosting vegetable siccative oil having a viscosity of not morethanabout 30 seconds on the Gardner-Holdt scale and an alpha betaethylenically unsaturated monocarboxylic acid while dispersed in ahydrocarbon solvent and copolymerizing the resulting ester with acompound consisting of a vinyl aromatic compound having a single vinylgroup in the presence of a hydrocarbon solvent at elevated temperaturesof about 60 C. to about 150 C.

4. A method of producing valuable polymers comprising esterifying amixture the reactive ingredients of which consist of an oxidizednonfrosting vegetable siccative oil having a viscosity of not more than30 seconds on the Gardner-Holdt scale and maleic acid and copolymerizingthe resulting ester with a compound consisting of a vinyl aromaticcompound having a single vinyl group at elevated temperatures of about60 C. to about 150 C.

5. A method of producing valuable polymers comprising esterifying amixture the reactive ingredients of which consist of an oxidizednonfrosting vegetable siccative oil having a viscosity of not more thanabout 30 seconds on the Gardner-Holdt scale and an alpha betaethylenically unsaturated carboxylic acid and copolymerizing theresulting ester with a compound consisting of styrene at elevatedtemperatures of about 60 C. to about 150 C.

6. A copolymer consisting of a vinyl aromatic compound having a singlevinyl group and an alpha beta ethylenically unsaturated carboxylic acidester of an oxidized nonfrosting vegetable siccative oil having aviscosity of not more than about 30 seconds on the Gardner- Holdt scale.

7. A copolymer consisting of a vinyl aromatic compound having a singlevinyl group of an alpha beta ethylenically unsaturated dicarboxylic acidester of an oxidized nonfrosting vegetable siccative oil having aviscosity of not more than about 30 seconds on the Gardner- Holdt scaleand a hydroxyl number of about 30 to about 50.

8. A copolymer consisting of a vinyl aromatic compound having a singlevinyl group and an alpha beta ethylenically unsaturated monocarboxylicacid ester of an oxidized nonfrosting vegetable siccative oil having aviscosity of not more than about 30 seconds on the Gardner-Holdt scaleand a hydroxyl number of about 30 to about 50.

9. A copolymer consisting of a vinyl aromatic compound having a singlevinyl group and an alpha beta ethylenically unsaturated carboxylic acidester of an oxidized linseed oil having a viscosity of not more thanabout 30 seconds on the Gardner-Holdt scale and a hydroxyl number ofabout 30 to about O.

10. A copolymer consisting of a vinyl aromatic compound having a singlevinyl group and an alpha beta ethylenically unsaturated carboxylic acidester of an oxidized soya bean oil having a viscosity of not more thanabout 30 seconds on the Gardner-Holdt scale and a hydroxyl number ofabout 30 to about 50.

11. A copolymer consisting of a vinyl aromatic compound having a singlevinyl group and a maleic acid ester of a linseed oil which has beenoxidized to a viscosity of not more than about 30 seconds on theGardner-Holdt scale and which has a hydroxyl number of about 30 to about50.

12. A copolymer consisting of a vinyl aromatic compound having a singlevinyl group and a maleic acid ester of a soya bean oil which has beenoxidized to a viscosity of not more than about 30 seconds on theGardner-Holdt scale and which has a hydroxyl number of about 30 to about50.

13. A copolymer consisting of styrene and the maleic acid ester ofoxidized linseed oil having a viscosity of not more than about 30seconds on the Gardner-Holdt scale and a hydroxyl number of about 30 toabout 50.

14. A copolymer consisting of a vinyl aromatic compound having a singlevinyl group and an alpha beta ethylenically unsaturated carboxylic acidester of an oxidized nonfrosting vegetable siccative oil having aviscosity of not more than about 30 seconds on the Gardner- Holdt scalecontaining at least about 35% by weight of at least one acid of thegroup consisting of linoleic and linolenic.

15. A copolymer consisting of about 33% to about 67% by Weight vinylaromatic compound having a single vinyl group and about 67% to about 33%by weight of the alpha beta ethylenically unsaturated carboxylic acidester of an oxidized nonfrosting vegetable siccative oil having aviscosity of not more than about 30 seconds on the Gardner-Holdt scale.

16. A copolymer consisting of about 50% by weight copolymerized vinylaromatic compound having a single vinyl group and about 50% by weightcopolymerized alpha beta ethylenically unsaturated carboxylic acid esterof oxidized nonfrosting vegetable siccative oil having a viscosity ofnot more than about 30 seconds on the Gardner-Holdt scale.

17. A copolymer consisting of about 33% to about 67% by weightcopolymerized styrene and about 67% to about 33% by weight of a maleicacid ester of oxidized linseed oil having a viscosity of not more thanabout 30 seconds on the Gardner-Holdt scale.

18. A copolymer consisting of about equal parts by Weight of styrene anda maleic acid ester of oxidized soya bean oil having a viscosity of notmore than about 30 seconds on the Gardner-Holdt scale.

19. A floor covering binder comprising a tackifying resin selected fromthe group consisting of ester gum, rosin-modified phenol-formaldehyderesin, and diethylene glycol ester of hydrogenated rosin and a copolymerconsisting of a vinyl aromatic compound having a single vinyl group andan alpha beta ethylenically unsaturated carboxylic acid ester of anoxidized nonfrosting vegetable siccative oil having a viscosity of notmore than about 30 seconds on the Gardner-Holdt scale.

20. A floor covering binder comprising about 5% to about 15% by weightof a tackifying resin selected from the group consisting of ester gum,rosin-modified phenolformaldehyde resin, and diethylene glycol ester ofhydrogenated rosin and about 95 to about by weight of a copolymer ofconsisting of a vinyl aromatic compound having a single vinyl group andan alpha beta ethylenicaly unsaturated carboxylic acid ester of anoxidized nonfrosting vegetable siccative oil having a viscosity of notmore than about 30 seconds on the Gardner- Holdt scale.

21. A floor covering binder comprising about 5% to about 15% by weightof ester gum and about to about 85% by weight of a copolymer consistingof styrene and a maleic acid ester of oxidized soya bean oil having aviscosity of not more than about 30 seconds on the Gardner-Holdt scale.

2,767,151 7 8 22. A floor covering binder comprising about 5% toviscosity of not more than about 30 seconds on the about 15% by weightof a diethylene glycol ester of hy- Gardner-I-Ioldt scale; drogenatedrosin and about 95% to' about 85% by weight of a copolymer consisting ofstyrene and a maleic acid Refefellces Cited in the l Of this P919111tester of oxidized soya bean oil having a viscosity of not 5 V UNITEDSTATES PATENTS more than about 30 seconds on the Gardner-Holdt scale.

23. A coating composition comprising a hydrocarbon g fi gz 25; solventand a copolymer consisting of a vinyl aromatic a compound having asingle vinyl group and analpha beta FOREIGN PATENTS ethylenicallyunsaturated carboxylic acid ester of an 10 609,749 Great Britain Oct 6,1948 oxidized nonfrosting vegetable siccative oil having a

19. A FLOOR COVERING BINDER COMPRISING A TACKIFYING RESIN SELECTED FROMTHE GROUP CONSISTING OF ESTER GUM, ROSIN-MODIFIED PHENOL-FORMALDEHYDERESIN, AND DIETHYLENE GLYCOL ESTER OF HYDROGENATED ROSIN AND A COPOLYMERCONSISTING OF A VINYL AROMATIC COMPOUND HAVING A SINGLE VINYL GROUP ANDAN ALPHA BETA ETHYLENICALLY UNSATURATED CARBOXYLIC ACID ESTER OF ANOXIDIZED NONFROSTING VEGETABLE SICCATIVE OIL HAVING A VISCOSITY OR NOTMORE THAN ABOUT 30 SECONDS ON THE GARDNER-HOLDT SCALE.